Within the sphere of (meth)acryloxy group-containing polyorganosiloxanes in which the (meth)acryloxy group, i.e., the methacryloxy group or the acryloxy group, is bonded to a silicon atom in a polyorganosiloxane across an alkylene group, polyorganosiloxanes are already known in which the alkylene group is methylene, propylene, or butylene.
Patent Reference 1 (JP 06-051795 B, U.S. Pat. No. 5,039,761) discloses a polydimethylsiloxane in which the methacryloxy group is bonded to the main chain via the propylene group, while Patent Reference 2 (JP 60-215009 A, U.S. Pat. No. 4,675,346) discloses a polydiorganosiloxane in which the (meth)acryloxy group is bonded across the propylene group to the silicon at both terminals.
A polyorganosiloxane in which the (meth)acryloxy group is bonded via the methylene group is reported in Nonpatent Reference 1 (Journal of Organic Chemistry (1961), 26, 5180-5182), while a polyorganosiloxane in which the (meth)acryloxy group is bonded via the butylene group is reported in Nonpatent Reference 2 (Neth. Appl. (1979), 40 pp CODEN: NAXXAN NL 7807833 19790129) and in Nonpatent Reference 3 (Zhurnal Obshchei Khimii (1979), 49 (10), 2250-4).
In addition, within the sphere of polyorganosiloxanes in which the methacryloxy group is bonded to silicon therein across an alkyleneoxyalkylene group, Patent Reference 3 (JP 61-050988 A) discloses a polyorganosiloxane in which this bonding occurs across an ethyleneoxypropylene group, while Patent Reference 4 (JP 08-231857 A) discloses a polyorganosiloxane in which this bonding occurs across a polyalkyleneoxyalkylene group wherein the alkylene group has 2 to 5 carbon atoms, although the examples here concern only polyorganosiloxanes in which this bonding occurs across a polyethyleneoxypropylene group. That is, polyorganosiloxane whose synthesizability is demonstrated by the examples is limited to polyorganosiloxane in which the methacryloxy group is bonded therein across the polyethyleneoxypropylene group.
On the other hand, within the sphere of monomers that can be used in a vinyl-type copolymerization, Patent Reference 5 (JP 10-512290 A, WO 1997/012588) discloses a macromonomer in which the (meth)acryloxy group is bonded to the silicon atom at one terminal of a polydimethylsiloxane by an alkylene group having 2 to 6 carbon atoms or alkyleneoxy group having 2 to 6 carbon atoms, but no description whatever of a method of producing this macromonomer is provided in Patent Reference 5.
Patent Reference 6 (JP 2000-186122 A, U.S. Pat. No. 6,090,902) discloses, again as a monomer that can be used in a vinyl-type copolymerization, a macromonomer in which the methacryloxy group is bonded to the silicon atom at one terminal of a polydimethylsiloxane across an alkylene group having 2 to 4 carbon atoms, but the synthesis examples here concern only macromonomer in which the methacryloxy group is bonded to the silicon at one terminal of a polydimethylsiloxane across the propylene group.
Patent Reference 7 (JP 2005-527666 A, WO 2003/085035) discloses, again as a monomer that can be used in a vinyl-type copolymerization, a macromonomer in which the methacryloxy group or acryloxy group is bonded to the silicon atom at one terminal of a polydimethylsiloxane via the propylene group, but no description whatever of a method of producing this macromonomer is provided in Patent Reference 7.
Patent Reference 8 (JP 2006-037109 A, FR 2873702 A1, EP 1621560 A1) discloses, again as a monomer that can be used in a vinyl-type copolymerization, a macromonomer in which the (meth)acryloxy group is bonded to the silicon atom at one terminal of a polydimethylsiloxane via an alkylene group having 1 to 10 carbon atoms that may contain one or two ether linkages, but no description whatever of a method of producing this macromonomer is provided in Patent Reference 8.
As described above, the preceding patent documents do not teach a macromonomer in which the (meth)acryloxy group, i.e., the methacryloxy group or acryloxy group, is bonded to the silicon atom at one terminal of a polydimethylsiloxane via a long-chain alkylene wherein the alkylene group that has at least 11 carbon atoms, and such a macromonomer has not appeared in a printed publication.
On the other hand, the preceding patent documents do not teach a macromonomer in which the (meth)acryloxy group, i.e., the methacryloxy group or acryloxy group, is bonded to the silicon atom at one terminal of a polydimethylsiloxane via a polyalkyleneoxyalkylene group wherein the total number of carbon atoms in both alkylene groups is at least 11, and such a macromonomer has not appeared in a printed publication.    [Patent Reference 1] JP 06-051795 B, U.S. Pat. No. 5,039,761    [Patent Reference 2] JP 60-215009 A, U.S. Pat. No. 4,675,346    [Patent Reference 3] JP 61-050988 A    [Patent Reference 4] JP 08-231857 A    [Patent Reference 5] JP 10-512290 A, WO 1997/012588    [Patent Reference 6] JP 2000-186122 A, U.S. Pat. No. 6,090,902    [Patent Reference 7] JP 2005-527666 A, WO 2003/085035    [Patent Reference 8] JP 2006-037109 A, FR 2873702 A1, EP 1621560 A1    [Nonpatent Reference 1] Journal of Organic Chemistry (1961), 26, 5180-5182    [Nonpatent Reference 2] Neth. Appl. (1979), 40 pp CODEN: NAXXAN NL 7807833 19790129    [Nonpatent Reference 3] Zhurnal Obshchei Khimii (1979), 49(10), 2250-2254
Methacryloxy group- or acryloxy group-containing polyorganosiloxanes are commonly used for the modification of various types of thermoplastic resins by the incorporation into the thermoplastic resin of the copolymer provided by copolymerization of such a polyorganosiloxane with another vinylic monomer utilizing the vinylic polymerizability of the methacryloxy group or acryloxy group. With regard to the methacryloxy group- or acryloxy group-containing polyorganosiloxanes that have generally been used for this copolymerization with another vinylic monomer, the present inventor recognized that the polysiloxanyl group, which is the group that provides the resin-modifying effect, has had a low degree of freedom in the thermoplastic resin because the methacryloxy group or acryloxy group, which is the vinylically polymerizable moiety, has been bonded to the polysiloxanyl group across the short propylene group, and further recognized that this causes the problem of an unsatisfactory surface segregation by the polysiloxanyl group.